CA2314243A1 - Hydroxy-functional polyether laminates - Google Patents
Hydroxy-functional polyether laminates Download PDFInfo
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- CA2314243A1 CA2314243A1 CA002314243A CA2314243A CA2314243A1 CA 2314243 A1 CA2314243 A1 CA 2314243A1 CA 002314243 A CA002314243 A CA 002314243A CA 2314243 A CA2314243 A CA 2314243A CA 2314243 A1 CA2314243 A1 CA 2314243A1
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- Prior art keywords
- layer
- hydroxy
- metal
- functional polyether
- laminate structure
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
Landscapes
- Laminated Bodies (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
- Wrappers (AREA)
Abstract
A laminate structure comprising one or more layers of a metal and one or more layers of a hydroxy-functional polyethers and, optionally, one or more layers of an organic polymer which is not a hydroxy-functional polyether. The laminate structures are useful in the manufacture of containers, such as aerosol containers and beverage containers.
Description
..z .1~,-ii,-a~ ~_ '~'o_t~ _: i'lLi ~'..'.;3 147t;-.r +49 89 2:3994465:#/ 4.
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V11~,V TI IT
f CA 02314243 2000-06-13 .
HYDR4XY-FUNCTtQNAt- P~l_YETHER t_AMiNATES
This invention relates to metal-polymer laminates useful for fabricating articles, such as beverage containers and aerosol containers.
Metal-p~alymer laminates are known and ate described, for example, in U.S. Patents 4.62&,157; 4,423;823; 4,034,132; 4,686,952; 4,734,303 and 4,361,020. The polymers employed in preparing the laminates include polyesters, polypropylene, polyethylene, poiycarbonate, polyimide and blends thereof. Films prepared from these polymers suffer from their inadequate adhesion to the metal, their inability to elongate during metal forming due to the highly oriented nature of the polymer film, and their n0 tendency to delaminate during forming andlor end-use application. Thin palyolefin-based films with polar comonomer adhesive layers, while offering good adhesion characteristics to metal, and good elongation during metal laminate forming, can suffer from inadequate IaminGte cuttabitity (resulting in coating "stringing"), and inadequate scratch resistance and end-use toughness.
It would be desirable to provide polymer films with such characteristics as adequate toughness, abrasion resistance, thermal stability, ductility, formability, good barrier properties and chemical resistance to many chemicals.
In a first aspect, the present invention is a laminate structure comprising one or more layers of a metal and one or more layers of a hydroxy-functional polyether .?0 and, optionally, one or more layers of an organic polymer which is not hydroxy-functional polyether.
In a second aspect, the present invention is a container comprising a laminate structure having one or more layers of a metal and one or more layers of a hydroxy-functional pol;rather and, optionally, one or more layers of an organic polymer :25 which is net hydroxy-functional polyether.
Preferably, the hydroxy-functional polyetherhydroxy-functional polyethers employed in the practice of the present invention for preparing the polymer iayer(s) are:
(1 ) hydroxy-functional polyethers having'repeating units represented by the formula:
OH
OCH2CCHzDA~ z R
n ~I~~li~lED SHEET
VV111. V~. L1'1~I VI ~1~lYVLaa'a~ aLl I V/ V-/ I V.Tf-, ~17L/CA jtT1 f ~I
V11~,V TI IT
f CA 02314243 2000-06-13 .
HYDR4XY-FUNCTtQNAt- P~l_YETHER t_AMiNATES
This invention relates to metal-polymer laminates useful for fabricating articles, such as beverage containers and aerosol containers.
Metal-p~alymer laminates are known and ate described, for example, in U.S. Patents 4.62&,157; 4,423;823; 4,034,132; 4,686,952; 4,734,303 and 4,361,020. The polymers employed in preparing the laminates include polyesters, polypropylene, polyethylene, poiycarbonate, polyimide and blends thereof. Films prepared from these polymers suffer from their inadequate adhesion to the metal, their inability to elongate during metal forming due to the highly oriented nature of the polymer film, and their n0 tendency to delaminate during forming andlor end-use application. Thin palyolefin-based films with polar comonomer adhesive layers, while offering good adhesion characteristics to metal, and good elongation during metal laminate forming, can suffer from inadequate IaminGte cuttabitity (resulting in coating "stringing"), and inadequate scratch resistance and end-use toughness.
It would be desirable to provide polymer films with such characteristics as adequate toughness, abrasion resistance, thermal stability, ductility, formability, good barrier properties and chemical resistance to many chemicals.
In a first aspect, the present invention is a laminate structure comprising one or more layers of a metal and one or more layers of a hydroxy-functional polyether .?0 and, optionally, one or more layers of an organic polymer which is not hydroxy-functional polyether.
In a second aspect, the present invention is a container comprising a laminate structure having one or more layers of a metal and one or more layers of a hydroxy-functional pol;rather and, optionally, one or more layers of an organic polymer :25 which is net hydroxy-functional polyether.
Preferably, the hydroxy-functional polyetherhydroxy-functional polyethers employed in the practice of the present invention for preparing the polymer iayer(s) are:
(1 ) hydroxy-functional polyethers having'repeating units represented by the formula:
OH
OCH2CCHzDA~ z R
n ~I~~li~lED SHEET
(2) amide- and hydroxymethyl-functional polyethers having repeating units represented by the formula:
OH OH
OCH2CCHZOArI OCHzCCH20Ar2 II
I R x ~ R
1-x n (3) hydroxy-functional poiy(ether sulfonamides) having repeating units represented by the formula:
OCHZCCHZN-IS-R~ SI-NCH2CCH20Ar IIIa I
R O O R
n or OH
OCHzCCH2-N-CH2 i CH20Ar I IIb O-SAO R
a n (4) poly(hydroxy amide ethers) having repeating units represented independently by any one of the following formulas:
OH O O
OCH2CCH20Ar-NHC-R1 CINHAr IVa I
R
n OCH2CCH20Ar-CNH-R1 NHCAr I~
I
R
n or OH O
OCH2CCH20ArCNHAr IVc I
R
n (5) poly(hydroxy ester ethers) having repeating units represented by the formula:
O OH O O CHZOH
Rl-C~O CHzCCH20R1 OCI-Rl-CIOC-CH
R R
~l-(x+y) y x (6) poly(hydroxy amide ethers) having repeating units represented by any one of the following formulas:
off o 0 off OCH2CCH20Ar-NHC-R1 CNH-Ar-OCH2~CH20Ar2 VIa R R
n OH O O OH
OCH2CCHZOAr-CNH-R1 NHC-Ar-OCH2~CH20Ar2 VIb R R
n or OCH2CCH20Ar-CNH-Ar--OCH2~CH20Ar2 VIc R R
n (7) poly(hydroxyamino ethers) having repeating units represented by the formula:
OH OH
OCH2 i CH2-A-CH2 i CH20Ar VI I
R R
n and (8) hydroxy-functional polyethers having repeating units represented by the formula:
OH OH
OCH2CCHz-X-CH2CCH20-Ar3 VIII
I
R R
n wherein each Ar individually represents a divalent aromatic moiety, substituted divalent aromatic moiety or heteroaromatic moiety, or a combination of different divalent aromatic moieties, substituted aromatic moieties or heteroaromatic moieties; R is individually hydrogen or a monovalent hydrocarbyl moiety; each Ar' is a divalent aromatic moiety or combination of divalent aromatic moieties bearing amide or hydroxymethyl groups; each Arz is the same or different than Ar and is individually a divalent aromatic moiety, substituted aromatic moiety or heteroaromatic moiety or a combination of different divalent aromatic moieties, substituted aromatic moieties or heteroaromatic moieties; R' is individually a predominantly hydrocarbylene moiety, such as a divalent aromatic moiety, substituted divalent aromatic moiety, divalent heteroaromatic moiety, divalent alkylene moiety, divalent substituted alkylene moiety or divalent heteroalkylene moiety or a combination of such moieties; R2 is individually a monovalent hydrocarbyl moiety; A is an amine moiety or a combination of different amine moieties; X is an amine, an arylenedioxy, an arylenedisulfonamido or an arylenedicarboxy moiety or combination of such moieties; and Are is a "cardo" moiety represented by any one of the following formulas:
R2 v ~ R1 or R2 ~ ~~Rz wherein Y is nil, a covalent bond, or a linking group, wherein suitable linking groups include, for example, an oxygen atom, a sulfur atom, a carbonyl atom, a sulfonyl group, or a methylene group or similar linkage; n is an integer from 10 to 1000; x is 0.01 to 1.0; and y is 0 to 0.5.
The term "predominantly hydrocarbylene" means a divalent radical that is predominantly hydrocarbon, but which optionally contains a minor amount of heteroatomic moiety such as oxygen, sulfur, imino, sulfonyl, or sulfoxyl.
The hydroxy-functional polyethers represented by Formula I can be prepared, for example, by allowing a diglycidyl ether or combination of diglycidyl ethers to react with a dihydric phenol or a combination of dihydric phenols using the process described in U.S. Patent 5,164,472. Alternatively, the hydroxy-functional polyethers are obtained by allowing a dihydric phenol or combination of dihydric phenols to react with an epihalohydrin by the process described by Reinking, Barnabeo and Hale in the Journal of Applied Polymer Science, Volume 7, page 2135 (1963).
The amide- and hydroxymethyl-functional polyethers represented by Formula II can be prepared, for example, by reacting the diglycidyl ethers, such as the diglycidyl ether of bisphenol A, with a dihydric phenol having pendant amido, N-substituted amido and/or hydroxyalkyi moieties, such as 2,2-bis(4-hydroxyphenyl)acetamide and 3,5-dihydroxybenzamide. These polyethers and their preparation are described in U.S. Patents 5,115,075 and 5,218,075.
The hydroxy-functional poly(ether sulfonamides) represented by Formula III
are prepared, for example, by polymerizing an N,N'-diaikyl or N,N'-diaryldisulfonamide with a diglycidyl ether as described in U.S. Patent 5,149,768.
The poly(hydroxy amide ethers) represented by Formula IV are prepared by contacting a bis(hydroxyphenylamido)alkane or arena, or a combination of 2 or more of these compounds, such as N,N'-bis(3-hydroxyphenyl) adipamide or N,N'-bis(3-hydroxyphenyl)glutaramide, with an epihalohydrin as described in U.S. Patent 5,134,218.
The poly(hydroxy ester ethers) represented by Formula V are prepared by reacting diglycidyl ethers of aliphatic or aromatic diacids, such as diglycidyl terephthalate, or diglycidyl ethers of dihydric phenols with, aliphatic or aromatic diacids such as adipic acid or isophthalic acid. These polyesters are described in U.S. Patent 5,171,820.
The poly(hydroxy amide ethers) represented by Formula VI are preferably prepared by contacting an N,N'-bis(hydroxyphenylamido)alkane or arena with a diglycidyl ether as described in U.S. Patents 5,089,588 and 5,143,998.
The polyetheramines represented by Formula VII are prepared by contacting one or more of the diglycidyl ethers of a dihydric phenol with an amine having two amine hydrogens under conditions sufficient to cause the amine moieties to react with epoxy moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties. These polyetheramines are described in U.S.
Patent5,275,853.
The hydroxy-functional polyethers represented by Formula VIII are prepared, for example, by contacting at least one dinucleophilic monomer with at least one diglycidyl ether of a cardo bisphenol, such as 9,9-bis(4-hydroxyphenyl)fluorene, phenolphthalein, or phenolphthalimidine or a substituted cardo bisphenol, such as a substituted bis(hydroxyphenyl)fluorene, a substituted phenolphthalein or a substituted phenolphthalimidine under conditions sufficient to cause the nucleophilic moieties of the dinucleophilic monomer to react with epoxy moieties to farm a polymer backbone containing pendant hydroxy moieties and ether, imino, amino, sulfonamido or ester linkages. These hydroxy-functional polyethers are described in U.S. Application Serial No.
131,110, filed October 1, 1993.
The hydroxy-functional polyethers commercially available from Phenoxy Associates, Inc. are suitable for use in the present invention. These hydroxy-functional polyethers are the condensation reaction products of a dihydric polynuclear phenol, such as bisphenol A, and an epihalohydrin and have the repeating units represented by Formula I wherein Ar is an isopropylidene diphenylene moiety. The process for preparing them are described in U.S. Patent 3,305,528.
Most preferably, the hydroxy-functional polyethers employed in the practice of the present invention are the polyetheramines represented by Formula VII.
Preferably, the hydroxy-functional polyethers exhibit a molecular weight of at least 20,000 but less than 100,000, and preferably at least 30,000 and less than 80,000.
Hydroxy-functional polyethers having low molecular weight or exceedingly high molecular weight are difficult to process and exhibit insufficient physical properties to form into flexible films or adequately wet-out and adhere to a metal substrate.
To improve the chemical resistance, hardness, thermal resistance or other performance characteristics of the hydroxy-functional polyethers, the polyethers can be modified by known copolymerization or graft copolymerization techniques or by cross-linking with ethylenically unsaturated dicarboxylic acid anhydride or anhydride precursor such as succinic or malefic anhydride; diisocyanates, or formaldehydes, such as phenol-, urea- or melamine formaldehyde. Such reactions (copolymerization, cross-linking) can be performed by a reactive extrusion process wherein the reactants are fed into and reacted in an extruder using the conditions described in U.S. Patent 4,612,156. Such reactions can also take place after the films or laminates are formed by thermal, moisture or UV-induced reactions.
Monolayer and multilayer films can be prepared from the hydroxy-functional poiyethers by using conventional extrusion techniques such as feedblock extrusion, multimanifold or die coextrusion or combinations of the two, or by slot-die casting or annular blown film extrusion; extrusion coating onto another substrate layer; or by solvent spraying or solution casting. Solution casting is a well known process and is described, for example, in the Plastics Engineering Handbook of the Society of the Plastics Industry, Inc, 4th Edition, page 448. Additionally, multiple plies of hydroxy-functional polyethers and/or other organic polymers can be adhered together via a conventional process such as hot-roll thermal lamination in order to produce a multi-ply structure. This lamination of multiple separate layers or plies is especially beneficial when significant melt viscosity differences between the _7_ . i v- is-~~ ._ -ys : ;s r : / 13 '?:z3 1476- +49 89 223994465 : # 5 ,..~. ;.~: .....~ ~,'; y;;.:""~,~ CA p2314243~ 2000-06-13'~~ ~,.".~ .~.t~~
~~~..., "~.. ~. u~., ,., ...
4335?
various layers prevent uniform coextrusion of the layers. The films can be subsequently oriented monoaxially, in the machine or transverse direction, or biaxially, in both machine and transverse directions, to further improve their physical properties, such as increased tensile strength and secant modulus and reduced elongation.
These fi property changes can be beneficial when stamping or cutting a polymer-metal laminate. In general, multilayer films can be formed from the hydroxy-functional polyethers of the present invention by coe:xtruding one or more layers of the hydroxy-functional pofyethers and one or more layers .of an organic polymer which is not a hydroxy-functional polyether.
Such multilayered structures, whether formed via coextrusidn, extncsion coating, liquid 1 (i coating or multl-ply lamination, can be beneficially used to achieve composite properties not attainable by monolayer film or multicomponent blends. One such example involves the use of coextrusion to add an organic adhesive layer to an otherwise poorly adhering hydroxy-functional polyether to bond the phenoxyether polymer to a metal substrate. In preparing the monolayer and multllayer films, thermoplastic poiyurethanes (TPU), 1 °i thermoplastic elastomer {TPE), polyester (PET), glyol-modified copolyester {PETG), polyolefins or other therrnoplastic resins can be blended with the hydroxy-functional polyether at levels of less than 50 weight percent end, preferably less than 30 weight percent, based on the weight of the hydroxy-functional polyether layer. These other polymers can be bJendes~ into the hydroxy-functional palyether in order to reduce 2C~ composition cast, to modify physical properties, barrier or permeability properties, or adhesion characteristics.
additives such as fillers, pigments, stabilizers, impact modifiers, plasticizers, carbon black, conductive metal particles, abrasives and lubricating polymers may be incorporated into the hydroxy-functional poiyether films. The method of 25 incorporating the additives is not critical. The additives can conveniently be added to the hydroxy-functional polyether prior to preparing the films. if the polymer is prepared in solid form, the additives can be added to th~ melt prior to preparing the films.
Preferably, the hydroxy-functional polyether films exhibit an ultimate tensile strength of at least 48.3 M Nlm~ (7,000 psi), a yield elongation of 4 to 1Q percent, an 34 ultimate elongation of SO to 400 percent arid a 2 percent secant modulus of at least 137x.0 M nilmZ (200,000 psi.) The relatively high tensile strength, high rnodulus and low elongation of the film allows the film laminate to be cut and stamped in a high speed die cutting operation without undesirable f:lm elongation and stringing over t#ie edge of the cut mete; laminate in an open-anon used to produce aerosol valve mounting cups. As used 35 herein, the term "stringing" refers to a partially attached polymeric coating fiber or "hair"
caused by the incomplete cutting of the metal _g_ ~;f~EC~L~~~ Se-~~ T
laminate coating. The tough, elongatable polymeric coating is stretched over the cut edge of the metal where it is partially cut off; leaving either a ragged edge of polymer or a thin partially detached polymer strip, hair, string or fiber. It is also desirable that the hydroxy-functional polyether film exhibits a minimum of 2.0 Ib/inch adhesion to a metal substrate, preferably a minimum of at least 3.0 Ib/inch.
The monolayer film comprises the hydroxy-functional polyether.
Organic polymers which are not hydroxy-functional polyethers can be adhered to one or both sides of the hydroxy-functional polyether film layer to produce a multilayer film. Thus, the multilayer film can be in the form of the following structures:
(1 ) a two-layer film comprising a first layer of the hydroxy-functional polyether and a second layer comprising an organic polymer which is not a hydroxy-functional polyether.
(2) a three-layer film comprising a first outer layer of an organic polymer, a core layer of the hydroxy-functional polyether and a second outer layer of an organic polymer which is the same as or different from the organic polymer of the first outer layer;
(3) a three-layer film comprising a first outer layer of the hydroxy-functional polyether, a core layer of an organic polymer which is not a hydroxy-functional polyether and a second outer layer of an arganic polymer which is the same as or different from the organic polymer of the core layer; or (4) a three-layer film comprising a first outer layer of the hydroxy-functional polyether, a core layer of an organic polymer which is not a hydroxy-functional polyether and a second outer layer of a hydroxy-functional polyether which is the same as or different from the hydroxy-functional polyether of the first outer layer.
Organic polymers which are not hydroxy-functional polyethers which can be employed in the practice of the present invention for preparing the multilayer film include crystalline thermoplastic polyesters, such as polyethylene terephthalate (PET), amorphous thermoplastic polyesters such as glycol modified polyester (PETG); polyamides, polyolefins, and [polyolefins] styrenics based on monovinyl aromatic monomers; carboxylic acid modified olefin copolymers, such as ethylene-acrylic acid and ethylene-methacrylic acid copolymers, and anhydride-modffied polymers, such as polyethylene grafted with malefic anhydride, ethylene-vinyl acetate-graffed with malefic anhydride and ethylene-butylacrylate-malefic anhydride terpolymer.
_g_ . _ _., ..~- .. s..., - au ~ lad :GG:3 14 !b--~ t~~ ~5 23994'465 : ~f E
VV111. Yr. LI711 VI 1 iVL.'_.. Vf 1~u LLV! 111'J, lit 1V/J.I .V.1V~ Js a.oa A~TII,I 411~.V Vf .t Polyssters and methods for their preparation are well known in the ark and referencr~ is made thereto for the purposes of this invention. For purposes of illustration and not limitation, reference is particularly made to pages 1-B2 of Volume 12 of the EncyGopedia of Polymer Science and Engineering, 1988 revision, Jahn Wiley 8~ Sons.
Polyamides which can be employed in the practice of the present invention include the various grades of nylon, such as nylon 6, nylon 6& and nylon 12.
Also included era lower rnQlecular weight and lower viscosity polyantide copolymers which are used as hot-melt adhesives and which are well known in the art and are commercially available from numerous suppliers.
Polyolefins which can ba employed in the practice of the present invention for preparing the multilayer laminate structure include polypropylene, polyethylene, anti oapolymers and blends thereof, as well as ethylene-propylenediene terpolymer$. Preferred poiyolefiins are polypropylene, linear high density polyethylene (Hf3PE), heterogeneously branched linear low density polyethylene (LLDPE) such as DOWLF~CzM polyethylene resin (a Trademark of The Dow Chemical Company) heterogeneously-branched ultra low linear density polyethylene (ULDPE) such as ATTANE'"' ULDPE (a xradsmark of The Dow Chemical Company); homogeneously-branched, linear ethylersela-olefin copolymers such as TAFMERTM (a trademark of Mitsui Petrochemicals Company Limited) and EXACTT"' (a trademark of Exxon Chemical Company); hornogenecrusly-branched, substantially linear ethylenela-olefin polymers such as AFFlNIT'YT'" (a Trademark of The Dow Chemical Company} and ENGAGE'" (a Trad6mark of du Pont Dow Elastomers l..L.G.) polyoletin elastomers, which can be prepared as disclosed in U.S. Patents 5,272,236 and 6,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymers such as PRiMAGdRT"" (Trademark of The Dow Chemical Company), and ethylene-vinyl acetate (EVA) copolymers such as ESCORENET'" polymers (a Trademark of F~ocon Chemical Company}, and ELVAX'~" (a Trademark of E.I. du Pont de Nemours & Co.). The mare preferred pofyolefins are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in alccordance with ASTM D-792) of 0.85 to O.JtiS glcc, a weight average molecular weight to number average molecular weight ratio (M~JM~) from 1.5 to 3.0, a measured melt index (measured in acGOrdance with ASTM D-1239 (19012.1fi)) of 0.01 to 100 g11~ min, and alt I,~llz of 6 to 20 (measured in accordance with ( 190/10)).
i~' = ..
_ _ .LT f v--~ ~~t:J 0.7 ~c7.7aJ'YtOL7 ~ 3f l v '. t l v V ~ ~ L P1 ~ 1 V I I 1 V V ~ I V L L V 1 1 1 V ~ ~ IyL. l I V I V J
I V . T V , l C L t l~ T/ T l f ~ l V y lr 1 1 I t In general, high density polyethylene (HDPE) has a density of at least about 0.94 grams per cubic centimetar (glcc) (ASTM Test Method p-1505). HD PE
is commonly -t 014-AMEfdDtD S~~' . . o ._t.s 1't IU-~ t&'J~ Li:l :f:~:1~J44s5: ~ a VV111. Vr. VflY1 V11 iVL _-~ -- V'~ ' LLV ~J~.Vn .L/ IV/VV IV.TT, JCLffA
j,Tlf,1 Vl~.r Vl .1 . CA 02314243 2000-06-13 i . 4:~3t~7 produced using techniques similar to the preparation of linear low density polyethylenes. Such techniques are described in U.S. Patents 2,825,721;
2,993,876; 3.250,825 and 4.204,050. The preferred HDP~ employed in the practice of the present invention has a density of from 0.94 to 0.99 glcc and a mail index of from 0.01 io 35 grams per 10 minutes as determined by ASTM Test Method D-1238.
Styrenics based on monovinyl aromatic monomers which can be employed in the practice of the present invention include polystyrene, poiymethylstyrene, styrene-acrylonitrile, styrene-malefic anhydride copolymers, styrenelmethyistyrene or styrene/chlorostyrene copoly-mars.
Other organic polymErs which can be employed in the practice of the present invention for preparing the multilayer film inGude polyhexamethylene adipamide, polycaprolactone, polyhexamethylene sebacamide, polyethylene 2,fi-naphthalate and polyethylene 1,5-naphthalate, poiytetramethylene 9 ,2-dioxybEnzoate and copolymers of ethylene terephthalate and ethylene isophthalate.
The thicknes$ of the monolayer or multilayer fllm is dependent on a number of factors, including the intended use, materials stared in the container, the length of storage prior to use and the specific composition employed in each layer of the laminate structure.
In general, the monoiayer film will have a thickness of from 2.5 to 250 Nm (0.1 to 10.0 mils), preferably from 5.08 to 121 Nm (0.2 to 5.0 mils) and most preferably. 10.2 to 25.1 Nm (0.4 to 1.0 mils). The muitifayer ~Im will have a total thickness of from 2.5 to 260 Nm (0.1 to 10.0 mils), preferably from 5.08 to 127 pm (0.2 to 5.0 mils); with the thickness of the hydroxy-functional polyether iayer~;s) aeing from 10 percent to 90 percent, and preferably 20 percent to 80 percent of the total film thickness.
The metals which can be employed in the practice of the present invention for preparing the polymer-metal or polymer-metal-polymer laminate include tin plate steel (TPS), tin-free steel (TFS), electrochrame-coated steel (~CruS), galvanised steel, high strength low alloy steel, stainless steel, copper-plated steel, copper and alurninurri. The preferred metals are tin plate steal and tin-free steel. Preferably, the metal is in the form of a flat sheet having two major surfaces.
3~J Far most metal packaging appiicatlans, the metal typically ranges from 76.2 to 508 um (3 to 20 mils) in thickness, although the hydroxy-functional polyether film can be adhered to any gauge metal. it is within the scope of this present invention to laminate the hydroxy-functional polyether film to thin metal foil such as 5.08 to 50.8 Nm (0.2 to 2 mil) aluminum foil used in flexible packaging.
A~~Ef~~E~ SI'~~~'~
The polymer-metal or polymer-metal-polymer laminates of the present invention can be prepared by conventional lamination techniques. As is known in the art, specific laminating techniques include thermal lamination, that is, whereby an inherently melt activated adhesive film is heated and melt-bonded to a metal substrate by means of heat and pressure; or liquid coating and laminating, that is, whereby a separate adhesive such as a solvent-borne or aqueous-based adhesive is applied to the polymeric film or metal substrate at a desired thickness, the liquid driven off by a drying oven, and combining the film and the metal with heat and pressure to bond the two layers together. In a similar fashion to liquid coating, a hot-melt adhesive can be melted and applied by means of slot die coating or roll coating onto either the film or the metal and joining the hero plies of film and metal together with pressure using the molten hot-melt adhesive to intimately bond the structure together, followed by cooling.
In general, a two-ply laminate comprising a polymer film layer and a metal layer can be prepared in accordance with the present invention by contacting one of the major surfaces of the metal layer with the polymer film at an elevated temperature with concurrent application of pressure. Similarly, a three-ply laminate comprising a polymer film layer, a metal layer and a palymer film layer is formed by applying to the remaining major surface of the metal layer another polymer film layer which is the same as or different from the other polymer film layer,.
The polymer-metal or polymer-metal-polymer laminates can have any one of the following structures:
(a) a two-ply laminate comprising a first layer of a hydroxy-functional polyether (hydroxy-functional polyether) and a second layer of a metal;
(b) a three-ply laminate comprising a first outer layer of an organic polymer which is not hydroxy-functianal polyether, a core layer of HPEE and a second outer layer of a metal;
(c) a three-ply laminate comprising a first outer layer of hydroxy-functional polyether, a core layer of an organic polymer which is not hydroxy-functional polyether and a second outer layer of a metal;
(d) a three-ply laminate comprising a first outer layer of a hydroxy-functional polyether, a core layer of a metal and a second outer layer of an organic polymer which is not a hydroxy-functional polyether; and (e) a three-ply laminate comprising a first outer layer of a co-extruded hydroxy-functional polyether/PETG film, a core layer of a metal and a second outer layer of an organic polymer which is not a hydroxy-functional polyether.
Preferably, the organic polymer which is not a hydroxy-functional polyether is polypropylene.
In the above structures, the organic polymer which is not a hydroxy-functional polyether (hydroxy-functional polyether) can be a blend of two or more different organic polymers.
The polymer-metal or polymer-metal-polymer laminates of the present invention are suitable for use in the manufacture of three-dimensional metal structures, such as, for example, aerosol containers and its various parts, where pressure sealing is obtained by forming a crimped edge with the polymeric layer tightly engaged between two layers of a steel sheet. Typically, an aerosol container comprises a can body or wall, which may be formed in one piece, or which may comprise a can body cylinder closed at its bottom end by an end member and at its top end by a domed cover member. The one-piece aerosol can body, or the domed cover member, has a mouth which is itself closed by a valve cup, carrying the aerosol dispensing valve. The valve cup is usually swaged or1 to the body. The polymer-metal or polymer-metal-polymer laminates of the present invention are particularly suitable for use in the manufacture of aerosol valve mounting cups, aerosol can domes and bottoms and can wall or body assembly.
In addition, the polymer-metal or polymer-metal-polymer laminates of the present invention may be employed in the preparation of other containers where a chemical, corrosion and pressure resistant seal is desired. Furthermore, in the manufacture of metal paint cans, the bottom of such cans may be stamped and formed from metal-polymer laminates and joined to the cylindrical sides of the can by formation of a crimped seal. The resulting seam is impervious to solvents and other chemicals shipped in the container and maintains a teak-proof seal. Formation of such metal cans using the components formed from the present metal-polymer laminate eliminates the need for separate application of a gasketing material such as an isoprene rubber around the perimeter of a circular-shaped blank and the curing thereof with its concomitant solvent emissions. Utilizing coated metals .. .. . ~ >.~_,- i.:.-as . ca ~ a~ : /~/~ ! 1:.3 a!'.r3 1476-. +49 89 ?3994465 : øt 9 yVIpL Vr. LI~.t VI~1 1~VL' I CA 02314243 2000-VV- L/ 1 V/ J.J 1 V.TT, ~LLtCI.
71'Tt ( ~p yyV J/ IT
433!7 according to the present invention strsamllnes the metal paint can manufacturing process" resulting in improved efficiency.
The polymer-metal laminates of the present invention can be desp-drawn into formed containers such as beverage containers or food packaging container; or metal bulk packaging containers. The thermoplastic nature of the hydroxy-functional polyethsr film allows the polymeric coating to sufficiently elongate and draw as the can structure is mechanically formed. Conventional thermoset coatings such as cured epoxy coatings are fairly brittle and will fracture upon significant elongation of the metal substrate, such as occurs during deep drawing of 1-piece can bodies.
Additionally, large metal structures such as domestic appliance shells can be fabricated from the polymer-metal laminates of the present invention.
Domestic appliances, which include refrigerator, washing maci~ine, clothes dryer, and dishwasher, require exterior and interior surface finishes that are adherable tn metal, and are forrnable, durable, scratch and abrasion resistant, solvent resistant, and aesthetically pleasing. A
18 hydroxy-functional poiyather (hydroxy-functional polyethar) film laminate can replace the cured solvent-based primer andlor paint finish typically used with preformed postpainted appliance shells. The ductility and formability of pigmented hydroxy-functional poiyether film-metal laminate permits the precoated coiled steel to be formed into the appliance shell without needing to be painted after forming."
The following Examples are for illustrative purposes only and are not intended to limit the scope of this invention. Unless otherwise indicated, all parts and percentages are by weight.
Exam~~te 1 A monolayer 0.8 mil (20 micron) hydroxy-phenoxyether (phenoxy~ film 2~ was producEd via conventional cast film extrusion using a phenoxy resin having a Tg of 100°C and a molecular weight of 50,000, available from Phenoxy Associates as Pa Phen PKFE. The film was extruded at a melt temperature of 228°C, quenched on a chill roll at E5°C, further cooled to 30°C, and wound into a film soil. The 20 micron film was then separately thermally larninated onto pre-heated 2fi7 micron (90.5 mil) tin plate steel at a 3~3 temperature of 204°C using a continuous cola metal lamination process and then quenched to room temperature using forced air cooling, followed by water-cooled chill rolls. The phenoxy film exhibits excellent adhesion to the metal and could not be delaminated from the m$tal without cohesive failure (tearing of the film at peel levels greater than 5.25 Nlcm (3.0 Ibllnch).
-14' ~tE~d~~D ~~~~~
w.ii~ uy. ,.n.. v. ~ yvi=-.. __ ..... ice. .r ~ .:y.uu . W~ ,'-~'v~.r.i~~Vu.T.r~ i+4J 89 2399~4~5~#10 CAV02314243 2.000-06-13 43.397 a le A two-layer coextrudad 15 micron (0.6 mil) film was produced from a glycol-modified copolyester (PETG), available from Eastman Chemical Company as PETG
fi783 resin and a phenoxy resin (PaPhen PKFE). A conventional multifayered cast film line was used. the PETG resin was extruded at a melt temperature of 225°C in one layer, while the phenoxy resin was extruded at 225°C In a second adjacent layer. The 15 miaon f~Jm comprises a fi0 percent PETG layer and 40 percent phenoxy layer, based on the film thickness. The coextruded iwo-layer frlrn was quenched on a chill roll at 85°C, further cooled to 30°G, and wound into a film roll. The 15 rrticron was then Thermally laminated onto pre-heated 267 micron (10.5 mil) tin plate steel at a temperature of 204°C (400°F) f with the phenoxy layer bonded to the metal and then quenched to room temperature using forced-air cooling followed by water-cooled shill rolls. The phenoxyIPETG film could not be delaminated from the metal without destructive tearing of the fclm.
t5 Physical Properties of Films of Example 1 8 2:
Film MDUW ~Ui6 niate MD% TD MD
lo lo Ultimate Tensile Tensile Yield Yi6ld Elongation (%) M t~;mZ M Wma ElongationElor~on(~) %
Ex. 69.0 55.2 9 fi 1 TO
si si Ex. S0, 0 37.2 $ _ ~ 170 8700 si 5400 si ?.0 Physical Properties of Films of Example 1 & 2 (continued):
f Film Tt?/ UIGrnateMD 2~ TD 2J MD Elm. TD Elm. Spencer ~Ongaton Secant Secant Tear Tear impact (%) ModuiusModules StrengthStrength (glNm) M Nlmz M Nlm2 ( I m ! m Ex 200 1909.9 18$,2.3 305 330 7't93 (ZT~r700p~i(273000 (12 9lmiJ)(13glmfl)(295 psi) g/mii 2A.0 1813.3 1703.6 1651 254 5$58 I
p~3oo0psi)(25~ooppsi)(65 Imil1d /rnil 270 mil -t 5-~~Ef~~lct~ S~c~'~
_ __ . sv~:~I _. f1J L.tJ 1'tWb-~ -r~~ ts~ :1:3J:j44fi5:~#~.1 V V . W V't . W ~1 V 1 1 i V L _~ ~ _ - a w 1... V V " V . L 1 1 V 1 J .J . V
. ~ J ~ ~tSL. tlr, ,j 1 1 f ~ 1 V 1j '- . I ! . t CA~02314243~2000-06-13 x r IP
The iwo-fayer phenoxyIPETG film of Example 2 was thermally laminated to a 7E~ micron (10.5 milt' tin plate steel at a temperature of 204°C
(40Q°F) with the PETG
layer contacting the preheated metal. The film exhibited excellent adhesion to the metal .5 and could not be delaminated.
~, a A monclayer film of a poly(hydroxy amino ether) (PNAE) resin was made on a conventional cast ~1rn line. The PHAE resin was prxluced from the reaction of the diglycidyl ether of bisphenol A (DGEBA) and monoethanolamlne (MEA) following the i0 procedure described in U.S. Patent 5,275.853, and had a Tg of 70°C
and a molecular weight of 60,000. The 12.7 micron (0.5 mil) film was ea~truded at a melt temperature of 210°C and quenched t~.n a cooled casting roll at 85°C, prior to being further quenched to 30°C and wound into a roll. The film was thermally laminated to a 2C7 micron (10.5 mil) tin plate steel, a s mil alurrdnum and a 6 mil ECCS at a temperature of 204°C. In ail three 15 cases, the PHAE film exhibits excellent adhesion to metal and could not be peeled from the metal.
xa a 5 d~tv~~o-layer coextrudad film of PHAE and ethylene-acrylic acid (9 percent AA) was made via conventional cast film coextrusian. Both resins were extruded at 21D°C
20 and quenches at 65°C prior to being further cooled to 30°C
and rolled into a film roll. The 25.4 micron (1.0 mil) film was produced with a layer ratio of 5t) percent of PHAE and 50 percent of ethylene-acrylic gad (AAA). The rtlm was then thermally laminated to a preheatEd tin plate steel at a04°C, with the EAA layer of the coextruded film contacting and adhering to the steel. The film exhibited tn excess of 5.25 Nlcm (3.0 Iblinch) adhesion 25 io the metal and could not be~ peeled without destruction of the film.
~.xample 6 .
A 15 micron (0.6 mi!) biaxially oriented polyester (OPET) ftlm was coated with a solvent-basal phenoxy solution (40 percent phenoxy solids in methyl-ethyl ketone, available from Phenoxy Associates as UCAR PKHS-a0). A conventional liquid water was 30 used to apply the wet liquid ;gating tv one site of the aPET film. The wet-coated film was than transported through 2 multizone hot air impingement drying oven (zone temperatures:
9a°i= to 150°F, 32°C to 55°C) to dry off the solvent, leaving a 5.08 pm (0.2 mil) solid phenoxy layer on the ~i:~t:ar7 ~t-t':.~ ( n av ~.-:~, 1~t tC~-~ t~J 23J :lii.~.y~~(jJ ~ # 1~
....., r ..~ . .~r~n u. . rv' . . _- _ _~ . v r.sy.... -iv . v, 1.1 . vI ....r . v.-wr, lvm pm . ,. .r.'y.. W
i 15 Nm (t3.6 mil) OPET film. The 20.3 Nm (0.8 mil) coated OPET film was ' then wound into a roll. The film was later thermally laminated onto pre-heated fin plate steel at 2p4°C using a coil metal lamination line, with the phenoxy layer adhEred to the metal surtace. The hot laminate was then quenched to room temperature using forced-air coolJng and water-cooled chill rolls.
xmle7 The metal laminates of Examples 1, 2, 3, 4, 5 and 6 were drawn and formed into a 33 mm diameter by 12 mrn deep cup using a Tinius Olsen Ductomatic BUP
200 metal forming press. Cups with the laminae thin film on the outside of the cup and with the laminate thin f.lm on the inside of the cup were produced. The thin films exhibitedexcellent adhesion to the formed metal with no film delamJnation observed.
Example 8 Multilayered metal laminates using the same phenoxy-based films of Examples 1,2,3 and 4 were produced with a eoextruded 183 Nm (7.2 mil) polypropylene (PP)-ultra linear low density polyethylene (ULLOPE) blend film simultaneously laminated onto the opposite side of the metal from the phenoxy-based film. The polypropylene film was a two-Layer coextrusion with a 50 percent PP and 54 percent ULLDPE main layer (85 percent of filrn gauge) and a malefic anhydride grafted polyethylene adhesive layer (15 percent of film gauge), which was made in accordance with the teachings of 2~~ U.S. Patent 5, 006,383. The 183Nm PP flm was laminated to the top side of a preheated 267 pm (10.5 mil) tin plate steel and the respective Example 1, 2, 3 or 4 phenoxy-based flrn of O.a to O.B mil gauge was laminated to the bottom bide of the steel.
Thermal lamination was conducted at 204°C on a continuous coil steel lamination coating process.
I~fter lamination, the two-sided coated steel was cooled, wound into a roll, and later slit to 2:5 desired widths. The slit narrow web arils were later stamped into intricately shaped 25 mm diameter aerosol valve mounting cups t~VMC) using a commercial continuous 14-station multidie press. Each of the laminated structures exhibited good formability and drawability and no signs of film delarnination. The aerosol valve mounting cups were then further converted into aerosol valve assemblies by the addition of a valve, actuator and stem 30 assembly using a ~rnmercial valve assembly operation.
tfl~f~~-~~.L..1 AS's~ILS-.~
OH OH
OCH2CCHZOArI OCHzCCH20Ar2 II
I R x ~ R
1-x n (3) hydroxy-functional poiy(ether sulfonamides) having repeating units represented by the formula:
OCHZCCHZN-IS-R~ SI-NCH2CCH20Ar IIIa I
R O O R
n or OH
OCHzCCH2-N-CH2 i CH20Ar I IIb O-SAO R
a n (4) poly(hydroxy amide ethers) having repeating units represented independently by any one of the following formulas:
OH O O
OCH2CCH20Ar-NHC-R1 CINHAr IVa I
R
n OCH2CCH20Ar-CNH-R1 NHCAr I~
I
R
n or OH O
OCH2CCH20ArCNHAr IVc I
R
n (5) poly(hydroxy ester ethers) having repeating units represented by the formula:
O OH O O CHZOH
Rl-C~O CHzCCH20R1 OCI-Rl-CIOC-CH
R R
~l-(x+y) y x (6) poly(hydroxy amide ethers) having repeating units represented by any one of the following formulas:
off o 0 off OCH2CCH20Ar-NHC-R1 CNH-Ar-OCH2~CH20Ar2 VIa R R
n OH O O OH
OCH2CCHZOAr-CNH-R1 NHC-Ar-OCH2~CH20Ar2 VIb R R
n or OCH2CCH20Ar-CNH-Ar--OCH2~CH20Ar2 VIc R R
n (7) poly(hydroxyamino ethers) having repeating units represented by the formula:
OH OH
OCH2 i CH2-A-CH2 i CH20Ar VI I
R R
n and (8) hydroxy-functional polyethers having repeating units represented by the formula:
OH OH
OCH2CCHz-X-CH2CCH20-Ar3 VIII
I
R R
n wherein each Ar individually represents a divalent aromatic moiety, substituted divalent aromatic moiety or heteroaromatic moiety, or a combination of different divalent aromatic moieties, substituted aromatic moieties or heteroaromatic moieties; R is individually hydrogen or a monovalent hydrocarbyl moiety; each Ar' is a divalent aromatic moiety or combination of divalent aromatic moieties bearing amide or hydroxymethyl groups; each Arz is the same or different than Ar and is individually a divalent aromatic moiety, substituted aromatic moiety or heteroaromatic moiety or a combination of different divalent aromatic moieties, substituted aromatic moieties or heteroaromatic moieties; R' is individually a predominantly hydrocarbylene moiety, such as a divalent aromatic moiety, substituted divalent aromatic moiety, divalent heteroaromatic moiety, divalent alkylene moiety, divalent substituted alkylene moiety or divalent heteroalkylene moiety or a combination of such moieties; R2 is individually a monovalent hydrocarbyl moiety; A is an amine moiety or a combination of different amine moieties; X is an amine, an arylenedioxy, an arylenedisulfonamido or an arylenedicarboxy moiety or combination of such moieties; and Are is a "cardo" moiety represented by any one of the following formulas:
R2 v ~ R1 or R2 ~ ~~Rz wherein Y is nil, a covalent bond, or a linking group, wherein suitable linking groups include, for example, an oxygen atom, a sulfur atom, a carbonyl atom, a sulfonyl group, or a methylene group or similar linkage; n is an integer from 10 to 1000; x is 0.01 to 1.0; and y is 0 to 0.5.
The term "predominantly hydrocarbylene" means a divalent radical that is predominantly hydrocarbon, but which optionally contains a minor amount of heteroatomic moiety such as oxygen, sulfur, imino, sulfonyl, or sulfoxyl.
The hydroxy-functional polyethers represented by Formula I can be prepared, for example, by allowing a diglycidyl ether or combination of diglycidyl ethers to react with a dihydric phenol or a combination of dihydric phenols using the process described in U.S. Patent 5,164,472. Alternatively, the hydroxy-functional polyethers are obtained by allowing a dihydric phenol or combination of dihydric phenols to react with an epihalohydrin by the process described by Reinking, Barnabeo and Hale in the Journal of Applied Polymer Science, Volume 7, page 2135 (1963).
The amide- and hydroxymethyl-functional polyethers represented by Formula II can be prepared, for example, by reacting the diglycidyl ethers, such as the diglycidyl ether of bisphenol A, with a dihydric phenol having pendant amido, N-substituted amido and/or hydroxyalkyi moieties, such as 2,2-bis(4-hydroxyphenyl)acetamide and 3,5-dihydroxybenzamide. These polyethers and their preparation are described in U.S. Patents 5,115,075 and 5,218,075.
The hydroxy-functional poly(ether sulfonamides) represented by Formula III
are prepared, for example, by polymerizing an N,N'-diaikyl or N,N'-diaryldisulfonamide with a diglycidyl ether as described in U.S. Patent 5,149,768.
The poly(hydroxy amide ethers) represented by Formula IV are prepared by contacting a bis(hydroxyphenylamido)alkane or arena, or a combination of 2 or more of these compounds, such as N,N'-bis(3-hydroxyphenyl) adipamide or N,N'-bis(3-hydroxyphenyl)glutaramide, with an epihalohydrin as described in U.S. Patent 5,134,218.
The poly(hydroxy ester ethers) represented by Formula V are prepared by reacting diglycidyl ethers of aliphatic or aromatic diacids, such as diglycidyl terephthalate, or diglycidyl ethers of dihydric phenols with, aliphatic or aromatic diacids such as adipic acid or isophthalic acid. These polyesters are described in U.S. Patent 5,171,820.
The poly(hydroxy amide ethers) represented by Formula VI are preferably prepared by contacting an N,N'-bis(hydroxyphenylamido)alkane or arena with a diglycidyl ether as described in U.S. Patents 5,089,588 and 5,143,998.
The polyetheramines represented by Formula VII are prepared by contacting one or more of the diglycidyl ethers of a dihydric phenol with an amine having two amine hydrogens under conditions sufficient to cause the amine moieties to react with epoxy moieties to form a polymer backbone having amine linkages, ether linkages and pendant hydroxyl moieties. These polyetheramines are described in U.S.
Patent5,275,853.
The hydroxy-functional polyethers represented by Formula VIII are prepared, for example, by contacting at least one dinucleophilic monomer with at least one diglycidyl ether of a cardo bisphenol, such as 9,9-bis(4-hydroxyphenyl)fluorene, phenolphthalein, or phenolphthalimidine or a substituted cardo bisphenol, such as a substituted bis(hydroxyphenyl)fluorene, a substituted phenolphthalein or a substituted phenolphthalimidine under conditions sufficient to cause the nucleophilic moieties of the dinucleophilic monomer to react with epoxy moieties to farm a polymer backbone containing pendant hydroxy moieties and ether, imino, amino, sulfonamido or ester linkages. These hydroxy-functional polyethers are described in U.S. Application Serial No.
131,110, filed October 1, 1993.
The hydroxy-functional polyethers commercially available from Phenoxy Associates, Inc. are suitable for use in the present invention. These hydroxy-functional polyethers are the condensation reaction products of a dihydric polynuclear phenol, such as bisphenol A, and an epihalohydrin and have the repeating units represented by Formula I wherein Ar is an isopropylidene diphenylene moiety. The process for preparing them are described in U.S. Patent 3,305,528.
Most preferably, the hydroxy-functional polyethers employed in the practice of the present invention are the polyetheramines represented by Formula VII.
Preferably, the hydroxy-functional polyethers exhibit a molecular weight of at least 20,000 but less than 100,000, and preferably at least 30,000 and less than 80,000.
Hydroxy-functional polyethers having low molecular weight or exceedingly high molecular weight are difficult to process and exhibit insufficient physical properties to form into flexible films or adequately wet-out and adhere to a metal substrate.
To improve the chemical resistance, hardness, thermal resistance or other performance characteristics of the hydroxy-functional polyethers, the polyethers can be modified by known copolymerization or graft copolymerization techniques or by cross-linking with ethylenically unsaturated dicarboxylic acid anhydride or anhydride precursor such as succinic or malefic anhydride; diisocyanates, or formaldehydes, such as phenol-, urea- or melamine formaldehyde. Such reactions (copolymerization, cross-linking) can be performed by a reactive extrusion process wherein the reactants are fed into and reacted in an extruder using the conditions described in U.S. Patent 4,612,156. Such reactions can also take place after the films or laminates are formed by thermal, moisture or UV-induced reactions.
Monolayer and multilayer films can be prepared from the hydroxy-functional poiyethers by using conventional extrusion techniques such as feedblock extrusion, multimanifold or die coextrusion or combinations of the two, or by slot-die casting or annular blown film extrusion; extrusion coating onto another substrate layer; or by solvent spraying or solution casting. Solution casting is a well known process and is described, for example, in the Plastics Engineering Handbook of the Society of the Plastics Industry, Inc, 4th Edition, page 448. Additionally, multiple plies of hydroxy-functional polyethers and/or other organic polymers can be adhered together via a conventional process such as hot-roll thermal lamination in order to produce a multi-ply structure. This lamination of multiple separate layers or plies is especially beneficial when significant melt viscosity differences between the _7_ . i v- is-~~ ._ -ys : ;s r : / 13 '?:z3 1476- +49 89 223994465 : # 5 ,..~. ;.~: .....~ ~,'; y;;.:""~,~ CA p2314243~ 2000-06-13'~~ ~,.".~ .~.t~~
~~~..., "~.. ~. u~., ,., ...
4335?
various layers prevent uniform coextrusion of the layers. The films can be subsequently oriented monoaxially, in the machine or transverse direction, or biaxially, in both machine and transverse directions, to further improve their physical properties, such as increased tensile strength and secant modulus and reduced elongation.
These fi property changes can be beneficial when stamping or cutting a polymer-metal laminate. In general, multilayer films can be formed from the hydroxy-functional polyethers of the present invention by coe:xtruding one or more layers of the hydroxy-functional pofyethers and one or more layers .of an organic polymer which is not a hydroxy-functional polyether.
Such multilayered structures, whether formed via coextrusidn, extncsion coating, liquid 1 (i coating or multl-ply lamination, can be beneficially used to achieve composite properties not attainable by monolayer film or multicomponent blends. One such example involves the use of coextrusion to add an organic adhesive layer to an otherwise poorly adhering hydroxy-functional polyether to bond the phenoxyether polymer to a metal substrate. In preparing the monolayer and multllayer films, thermoplastic poiyurethanes (TPU), 1 °i thermoplastic elastomer {TPE), polyester (PET), glyol-modified copolyester {PETG), polyolefins or other therrnoplastic resins can be blended with the hydroxy-functional polyether at levels of less than 50 weight percent end, preferably less than 30 weight percent, based on the weight of the hydroxy-functional polyether layer. These other polymers can be bJendes~ into the hydroxy-functional palyether in order to reduce 2C~ composition cast, to modify physical properties, barrier or permeability properties, or adhesion characteristics.
additives such as fillers, pigments, stabilizers, impact modifiers, plasticizers, carbon black, conductive metal particles, abrasives and lubricating polymers may be incorporated into the hydroxy-functional poiyether films. The method of 25 incorporating the additives is not critical. The additives can conveniently be added to the hydroxy-functional polyether prior to preparing the films. if the polymer is prepared in solid form, the additives can be added to th~ melt prior to preparing the films.
Preferably, the hydroxy-functional polyether films exhibit an ultimate tensile strength of at least 48.3 M Nlm~ (7,000 psi), a yield elongation of 4 to 1Q percent, an 34 ultimate elongation of SO to 400 percent arid a 2 percent secant modulus of at least 137x.0 M nilmZ (200,000 psi.) The relatively high tensile strength, high rnodulus and low elongation of the film allows the film laminate to be cut and stamped in a high speed die cutting operation without undesirable f:lm elongation and stringing over t#ie edge of the cut mete; laminate in an open-anon used to produce aerosol valve mounting cups. As used 35 herein, the term "stringing" refers to a partially attached polymeric coating fiber or "hair"
caused by the incomplete cutting of the metal _g_ ~;f~EC~L~~~ Se-~~ T
laminate coating. The tough, elongatable polymeric coating is stretched over the cut edge of the metal where it is partially cut off; leaving either a ragged edge of polymer or a thin partially detached polymer strip, hair, string or fiber. It is also desirable that the hydroxy-functional polyether film exhibits a minimum of 2.0 Ib/inch adhesion to a metal substrate, preferably a minimum of at least 3.0 Ib/inch.
The monolayer film comprises the hydroxy-functional polyether.
Organic polymers which are not hydroxy-functional polyethers can be adhered to one or both sides of the hydroxy-functional polyether film layer to produce a multilayer film. Thus, the multilayer film can be in the form of the following structures:
(1 ) a two-layer film comprising a first layer of the hydroxy-functional polyether and a second layer comprising an organic polymer which is not a hydroxy-functional polyether.
(2) a three-layer film comprising a first outer layer of an organic polymer, a core layer of the hydroxy-functional polyether and a second outer layer of an organic polymer which is the same as or different from the organic polymer of the first outer layer;
(3) a three-layer film comprising a first outer layer of the hydroxy-functional polyether, a core layer of an organic polymer which is not a hydroxy-functional polyether and a second outer layer of an arganic polymer which is the same as or different from the organic polymer of the core layer; or (4) a three-layer film comprising a first outer layer of the hydroxy-functional polyether, a core layer of an organic polymer which is not a hydroxy-functional polyether and a second outer layer of a hydroxy-functional polyether which is the same as or different from the hydroxy-functional polyether of the first outer layer.
Organic polymers which are not hydroxy-functional polyethers which can be employed in the practice of the present invention for preparing the multilayer film include crystalline thermoplastic polyesters, such as polyethylene terephthalate (PET), amorphous thermoplastic polyesters such as glycol modified polyester (PETG); polyamides, polyolefins, and [polyolefins] styrenics based on monovinyl aromatic monomers; carboxylic acid modified olefin copolymers, such as ethylene-acrylic acid and ethylene-methacrylic acid copolymers, and anhydride-modffied polymers, such as polyethylene grafted with malefic anhydride, ethylene-vinyl acetate-graffed with malefic anhydride and ethylene-butylacrylate-malefic anhydride terpolymer.
_g_ . _ _., ..~- .. s..., - au ~ lad :GG:3 14 !b--~ t~~ ~5 23994'465 : ~f E
VV111. Yr. LI711 VI 1 iVL.'_.. Vf 1~u LLV! 111'J, lit 1V/J.I .V.1V~ Js a.oa A~TII,I 411~.V Vf .t Polyssters and methods for their preparation are well known in the ark and referencr~ is made thereto for the purposes of this invention. For purposes of illustration and not limitation, reference is particularly made to pages 1-B2 of Volume 12 of the EncyGopedia of Polymer Science and Engineering, 1988 revision, Jahn Wiley 8~ Sons.
Polyamides which can be employed in the practice of the present invention include the various grades of nylon, such as nylon 6, nylon 6& and nylon 12.
Also included era lower rnQlecular weight and lower viscosity polyantide copolymers which are used as hot-melt adhesives and which are well known in the art and are commercially available from numerous suppliers.
Polyolefins which can ba employed in the practice of the present invention for preparing the multilayer laminate structure include polypropylene, polyethylene, anti oapolymers and blends thereof, as well as ethylene-propylenediene terpolymer$. Preferred poiyolefiins are polypropylene, linear high density polyethylene (Hf3PE), heterogeneously branched linear low density polyethylene (LLDPE) such as DOWLF~CzM polyethylene resin (a Trademark of The Dow Chemical Company) heterogeneously-branched ultra low linear density polyethylene (ULDPE) such as ATTANE'"' ULDPE (a xradsmark of The Dow Chemical Company); homogeneously-branched, linear ethylersela-olefin copolymers such as TAFMERTM (a trademark of Mitsui Petrochemicals Company Limited) and EXACTT"' (a trademark of Exxon Chemical Company); hornogenecrusly-branched, substantially linear ethylenela-olefin polymers such as AFFlNIT'YT'" (a Trademark of The Dow Chemical Company} and ENGAGE'" (a Trad6mark of du Pont Dow Elastomers l..L.G.) polyoletin elastomers, which can be prepared as disclosed in U.S. Patents 5,272,236 and 6,278,272; and high pressure, free radical polymerized ethylene polymers and copolymers such as low density polyethylene (LDPE), ethylene-acrylic acid (EAA) copolymers such as PRiMAGdRT"" (Trademark of The Dow Chemical Company), and ethylene-vinyl acetate (EVA) copolymers such as ESCORENET'" polymers (a Trademark of F~ocon Chemical Company}, and ELVAX'~" (a Trademark of E.I. du Pont de Nemours & Co.). The mare preferred pofyolefins are the homogeneously-branched linear and substantially linear ethylene copolymers with a density (measured in alccordance with ASTM D-792) of 0.85 to O.JtiS glcc, a weight average molecular weight to number average molecular weight ratio (M~JM~) from 1.5 to 3.0, a measured melt index (measured in acGOrdance with ASTM D-1239 (19012.1fi)) of 0.01 to 100 g11~ min, and alt I,~llz of 6 to 20 (measured in accordance with ( 190/10)).
i~' = ..
_ _ .LT f v--~ ~~t:J 0.7 ~c7.7aJ'YtOL7 ~ 3f l v '. t l v V ~ ~ L P1 ~ 1 V I I 1 V V ~ I V L L V 1 1 1 V ~ ~ IyL. l I V I V J
I V . T V , l C L t l~ T/ T l f ~ l V y lr 1 1 I t In general, high density polyethylene (HDPE) has a density of at least about 0.94 grams per cubic centimetar (glcc) (ASTM Test Method p-1505). HD PE
is commonly -t 014-AMEfdDtD S~~' . . o ._t.s 1't IU-~ t&'J~ Li:l :f:~:1~J44s5: ~ a VV111. Vr. VflY1 V11 iVL _-~ -- V'~ ' LLV ~J~.Vn .L/ IV/VV IV.TT, JCLffA
j,Tlf,1 Vl~.r Vl .1 . CA 02314243 2000-06-13 i . 4:~3t~7 produced using techniques similar to the preparation of linear low density polyethylenes. Such techniques are described in U.S. Patents 2,825,721;
2,993,876; 3.250,825 and 4.204,050. The preferred HDP~ employed in the practice of the present invention has a density of from 0.94 to 0.99 glcc and a mail index of from 0.01 io 35 grams per 10 minutes as determined by ASTM Test Method D-1238.
Styrenics based on monovinyl aromatic monomers which can be employed in the practice of the present invention include polystyrene, poiymethylstyrene, styrene-acrylonitrile, styrene-malefic anhydride copolymers, styrenelmethyistyrene or styrene/chlorostyrene copoly-mars.
Other organic polymErs which can be employed in the practice of the present invention for preparing the multilayer film inGude polyhexamethylene adipamide, polycaprolactone, polyhexamethylene sebacamide, polyethylene 2,fi-naphthalate and polyethylene 1,5-naphthalate, poiytetramethylene 9 ,2-dioxybEnzoate and copolymers of ethylene terephthalate and ethylene isophthalate.
The thicknes$ of the monolayer or multilayer fllm is dependent on a number of factors, including the intended use, materials stared in the container, the length of storage prior to use and the specific composition employed in each layer of the laminate structure.
In general, the monoiayer film will have a thickness of from 2.5 to 250 Nm (0.1 to 10.0 mils), preferably from 5.08 to 121 Nm (0.2 to 5.0 mils) and most preferably. 10.2 to 25.1 Nm (0.4 to 1.0 mils). The muitifayer ~Im will have a total thickness of from 2.5 to 260 Nm (0.1 to 10.0 mils), preferably from 5.08 to 127 pm (0.2 to 5.0 mils); with the thickness of the hydroxy-functional polyether iayer~;s) aeing from 10 percent to 90 percent, and preferably 20 percent to 80 percent of the total film thickness.
The metals which can be employed in the practice of the present invention for preparing the polymer-metal or polymer-metal-polymer laminate include tin plate steel (TPS), tin-free steel (TFS), electrochrame-coated steel (~CruS), galvanised steel, high strength low alloy steel, stainless steel, copper-plated steel, copper and alurninurri. The preferred metals are tin plate steal and tin-free steel. Preferably, the metal is in the form of a flat sheet having two major surfaces.
3~J Far most metal packaging appiicatlans, the metal typically ranges from 76.2 to 508 um (3 to 20 mils) in thickness, although the hydroxy-functional polyether film can be adhered to any gauge metal. it is within the scope of this present invention to laminate the hydroxy-functional polyether film to thin metal foil such as 5.08 to 50.8 Nm (0.2 to 2 mil) aluminum foil used in flexible packaging.
A~~Ef~~E~ SI'~~~'~
The polymer-metal or polymer-metal-polymer laminates of the present invention can be prepared by conventional lamination techniques. As is known in the art, specific laminating techniques include thermal lamination, that is, whereby an inherently melt activated adhesive film is heated and melt-bonded to a metal substrate by means of heat and pressure; or liquid coating and laminating, that is, whereby a separate adhesive such as a solvent-borne or aqueous-based adhesive is applied to the polymeric film or metal substrate at a desired thickness, the liquid driven off by a drying oven, and combining the film and the metal with heat and pressure to bond the two layers together. In a similar fashion to liquid coating, a hot-melt adhesive can be melted and applied by means of slot die coating or roll coating onto either the film or the metal and joining the hero plies of film and metal together with pressure using the molten hot-melt adhesive to intimately bond the structure together, followed by cooling.
In general, a two-ply laminate comprising a polymer film layer and a metal layer can be prepared in accordance with the present invention by contacting one of the major surfaces of the metal layer with the polymer film at an elevated temperature with concurrent application of pressure. Similarly, a three-ply laminate comprising a polymer film layer, a metal layer and a palymer film layer is formed by applying to the remaining major surface of the metal layer another polymer film layer which is the same as or different from the other polymer film layer,.
The polymer-metal or polymer-metal-polymer laminates can have any one of the following structures:
(a) a two-ply laminate comprising a first layer of a hydroxy-functional polyether (hydroxy-functional polyether) and a second layer of a metal;
(b) a three-ply laminate comprising a first outer layer of an organic polymer which is not hydroxy-functianal polyether, a core layer of HPEE and a second outer layer of a metal;
(c) a three-ply laminate comprising a first outer layer of hydroxy-functional polyether, a core layer of an organic polymer which is not hydroxy-functional polyether and a second outer layer of a metal;
(d) a three-ply laminate comprising a first outer layer of a hydroxy-functional polyether, a core layer of a metal and a second outer layer of an organic polymer which is not a hydroxy-functional polyether; and (e) a three-ply laminate comprising a first outer layer of a co-extruded hydroxy-functional polyether/PETG film, a core layer of a metal and a second outer layer of an organic polymer which is not a hydroxy-functional polyether.
Preferably, the organic polymer which is not a hydroxy-functional polyether is polypropylene.
In the above structures, the organic polymer which is not a hydroxy-functional polyether (hydroxy-functional polyether) can be a blend of two or more different organic polymers.
The polymer-metal or polymer-metal-polymer laminates of the present invention are suitable for use in the manufacture of three-dimensional metal structures, such as, for example, aerosol containers and its various parts, where pressure sealing is obtained by forming a crimped edge with the polymeric layer tightly engaged between two layers of a steel sheet. Typically, an aerosol container comprises a can body or wall, which may be formed in one piece, or which may comprise a can body cylinder closed at its bottom end by an end member and at its top end by a domed cover member. The one-piece aerosol can body, or the domed cover member, has a mouth which is itself closed by a valve cup, carrying the aerosol dispensing valve. The valve cup is usually swaged or1 to the body. The polymer-metal or polymer-metal-polymer laminates of the present invention are particularly suitable for use in the manufacture of aerosol valve mounting cups, aerosol can domes and bottoms and can wall or body assembly.
In addition, the polymer-metal or polymer-metal-polymer laminates of the present invention may be employed in the preparation of other containers where a chemical, corrosion and pressure resistant seal is desired. Furthermore, in the manufacture of metal paint cans, the bottom of such cans may be stamped and formed from metal-polymer laminates and joined to the cylindrical sides of the can by formation of a crimped seal. The resulting seam is impervious to solvents and other chemicals shipped in the container and maintains a teak-proof seal. Formation of such metal cans using the components formed from the present metal-polymer laminate eliminates the need for separate application of a gasketing material such as an isoprene rubber around the perimeter of a circular-shaped blank and the curing thereof with its concomitant solvent emissions. Utilizing coated metals .. .. . ~ >.~_,- i.:.-as . ca ~ a~ : /~/~ ! 1:.3 a!'.r3 1476-. +49 89 ?3994465 : øt 9 yVIpL Vr. LI~.t VI~1 1~VL' I CA 02314243 2000-VV- L/ 1 V/ J.J 1 V.TT, ~LLtCI.
71'Tt ( ~p yyV J/ IT
433!7 according to the present invention strsamllnes the metal paint can manufacturing process" resulting in improved efficiency.
The polymer-metal laminates of the present invention can be desp-drawn into formed containers such as beverage containers or food packaging container; or metal bulk packaging containers. The thermoplastic nature of the hydroxy-functional polyethsr film allows the polymeric coating to sufficiently elongate and draw as the can structure is mechanically formed. Conventional thermoset coatings such as cured epoxy coatings are fairly brittle and will fracture upon significant elongation of the metal substrate, such as occurs during deep drawing of 1-piece can bodies.
Additionally, large metal structures such as domestic appliance shells can be fabricated from the polymer-metal laminates of the present invention.
Domestic appliances, which include refrigerator, washing maci~ine, clothes dryer, and dishwasher, require exterior and interior surface finishes that are adherable tn metal, and are forrnable, durable, scratch and abrasion resistant, solvent resistant, and aesthetically pleasing. A
18 hydroxy-functional poiyather (hydroxy-functional polyethar) film laminate can replace the cured solvent-based primer andlor paint finish typically used with preformed postpainted appliance shells. The ductility and formability of pigmented hydroxy-functional poiyether film-metal laminate permits the precoated coiled steel to be formed into the appliance shell without needing to be painted after forming."
The following Examples are for illustrative purposes only and are not intended to limit the scope of this invention. Unless otherwise indicated, all parts and percentages are by weight.
Exam~~te 1 A monolayer 0.8 mil (20 micron) hydroxy-phenoxyether (phenoxy~ film 2~ was producEd via conventional cast film extrusion using a phenoxy resin having a Tg of 100°C and a molecular weight of 50,000, available from Phenoxy Associates as Pa Phen PKFE. The film was extruded at a melt temperature of 228°C, quenched on a chill roll at E5°C, further cooled to 30°C, and wound into a film soil. The 20 micron film was then separately thermally larninated onto pre-heated 2fi7 micron (90.5 mil) tin plate steel at a 3~3 temperature of 204°C using a continuous cola metal lamination process and then quenched to room temperature using forced air cooling, followed by water-cooled chill rolls. The phenoxy film exhibits excellent adhesion to the metal and could not be delaminated from the m$tal without cohesive failure (tearing of the film at peel levels greater than 5.25 Nlcm (3.0 Ibllnch).
-14' ~tE~d~~D ~~~~~
w.ii~ uy. ,.n.. v. ~ yvi=-.. __ ..... ice. .r ~ .:y.uu . W~ ,'-~'v~.r.i~~Vu.T.r~ i+4J 89 2399~4~5~#10 CAV02314243 2.000-06-13 43.397 a le A two-layer coextrudad 15 micron (0.6 mil) film was produced from a glycol-modified copolyester (PETG), available from Eastman Chemical Company as PETG
fi783 resin and a phenoxy resin (PaPhen PKFE). A conventional multifayered cast film line was used. the PETG resin was extruded at a melt temperature of 225°C in one layer, while the phenoxy resin was extruded at 225°C In a second adjacent layer. The 15 miaon f~Jm comprises a fi0 percent PETG layer and 40 percent phenoxy layer, based on the film thickness. The coextruded iwo-layer frlrn was quenched on a chill roll at 85°C, further cooled to 30°G, and wound into a film roll. The 15 rrticron was then Thermally laminated onto pre-heated 267 micron (10.5 mil) tin plate steel at a temperature of 204°C (400°F) f with the phenoxy layer bonded to the metal and then quenched to room temperature using forced-air cooling followed by water-cooled shill rolls. The phenoxyIPETG film could not be delaminated from the metal without destructive tearing of the fclm.
t5 Physical Properties of Films of Example 1 8 2:
Film MDUW ~Ui6 niate MD% TD MD
lo lo Ultimate Tensile Tensile Yield Yi6ld Elongation (%) M t~;mZ M Wma ElongationElor~on(~) %
Ex. 69.0 55.2 9 fi 1 TO
si si Ex. S0, 0 37.2 $ _ ~ 170 8700 si 5400 si ?.0 Physical Properties of Films of Example 1 & 2 (continued):
f Film Tt?/ UIGrnateMD 2~ TD 2J MD Elm. TD Elm. Spencer ~Ongaton Secant Secant Tear Tear impact (%) ModuiusModules StrengthStrength (glNm) M Nlmz M Nlm2 ( I m ! m Ex 200 1909.9 18$,2.3 305 330 7't93 (ZT~r700p~i(273000 (12 9lmiJ)(13glmfl)(295 psi) g/mii 2A.0 1813.3 1703.6 1651 254 5$58 I
p~3oo0psi)(25~ooppsi)(65 Imil1d /rnil 270 mil -t 5-~~Ef~~lct~ S~c~'~
_ __ . sv~:~I _. f1J L.tJ 1'tWb-~ -r~~ ts~ :1:3J:j44fi5:~#~.1 V V . W V't . W ~1 V 1 1 i V L _~ ~ _ - a w 1... V V " V . L 1 1 V 1 J .J . V
. ~ J ~ ~tSL. tlr, ,j 1 1 f ~ 1 V 1j '- . I ! . t CA~02314243~2000-06-13 x r IP
The iwo-fayer phenoxyIPETG film of Example 2 was thermally laminated to a 7E~ micron (10.5 milt' tin plate steel at a temperature of 204°C
(40Q°F) with the PETG
layer contacting the preheated metal. The film exhibited excellent adhesion to the metal .5 and could not be delaminated.
~, a A monclayer film of a poly(hydroxy amino ether) (PNAE) resin was made on a conventional cast ~1rn line. The PHAE resin was prxluced from the reaction of the diglycidyl ether of bisphenol A (DGEBA) and monoethanolamlne (MEA) following the i0 procedure described in U.S. Patent 5,275.853, and had a Tg of 70°C
and a molecular weight of 60,000. The 12.7 micron (0.5 mil) film was ea~truded at a melt temperature of 210°C and quenched t~.n a cooled casting roll at 85°C, prior to being further quenched to 30°C and wound into a roll. The film was thermally laminated to a 2C7 micron (10.5 mil) tin plate steel, a s mil alurrdnum and a 6 mil ECCS at a temperature of 204°C. In ail three 15 cases, the PHAE film exhibits excellent adhesion to metal and could not be peeled from the metal.
xa a 5 d~tv~~o-layer coextrudad film of PHAE and ethylene-acrylic acid (9 percent AA) was made via conventional cast film coextrusian. Both resins were extruded at 21D°C
20 and quenches at 65°C prior to being further cooled to 30°C
and rolled into a film roll. The 25.4 micron (1.0 mil) film was produced with a layer ratio of 5t) percent of PHAE and 50 percent of ethylene-acrylic gad (AAA). The rtlm was then thermally laminated to a preheatEd tin plate steel at a04°C, with the EAA layer of the coextruded film contacting and adhering to the steel. The film exhibited tn excess of 5.25 Nlcm (3.0 Iblinch) adhesion 25 io the metal and could not be~ peeled without destruction of the film.
~.xample 6 .
A 15 micron (0.6 mi!) biaxially oriented polyester (OPET) ftlm was coated with a solvent-basal phenoxy solution (40 percent phenoxy solids in methyl-ethyl ketone, available from Phenoxy Associates as UCAR PKHS-a0). A conventional liquid water was 30 used to apply the wet liquid ;gating tv one site of the aPET film. The wet-coated film was than transported through 2 multizone hot air impingement drying oven (zone temperatures:
9a°i= to 150°F, 32°C to 55°C) to dry off the solvent, leaving a 5.08 pm (0.2 mil) solid phenoxy layer on the ~i:~t:ar7 ~t-t':.~ ( n av ~.-:~, 1~t tC~-~ t~J 23J :lii.~.y~~(jJ ~ # 1~
....., r ..~ . .~r~n u. . rv' . . _- _ _~ . v r.sy.... -iv . v, 1.1 . vI ....r . v.-wr, lvm pm . ,. .r.'y.. W
i 15 Nm (t3.6 mil) OPET film. The 20.3 Nm (0.8 mil) coated OPET film was ' then wound into a roll. The film was later thermally laminated onto pre-heated fin plate steel at 2p4°C using a coil metal lamination line, with the phenoxy layer adhEred to the metal surtace. The hot laminate was then quenched to room temperature using forced-air coolJng and water-cooled chill rolls.
xmle7 The metal laminates of Examples 1, 2, 3, 4, 5 and 6 were drawn and formed into a 33 mm diameter by 12 mrn deep cup using a Tinius Olsen Ductomatic BUP
200 metal forming press. Cups with the laminae thin film on the outside of the cup and with the laminate thin f.lm on the inside of the cup were produced. The thin films exhibitedexcellent adhesion to the formed metal with no film delamJnation observed.
Example 8 Multilayered metal laminates using the same phenoxy-based films of Examples 1,2,3 and 4 were produced with a eoextruded 183 Nm (7.2 mil) polypropylene (PP)-ultra linear low density polyethylene (ULLOPE) blend film simultaneously laminated onto the opposite side of the metal from the phenoxy-based film. The polypropylene film was a two-Layer coextrusion with a 50 percent PP and 54 percent ULLDPE main layer (85 percent of filrn gauge) and a malefic anhydride grafted polyethylene adhesive layer (15 percent of film gauge), which was made in accordance with the teachings of 2~~ U.S. Patent 5, 006,383. The 183Nm PP flm was laminated to the top side of a preheated 267 pm (10.5 mil) tin plate steel and the respective Example 1, 2, 3 or 4 phenoxy-based flrn of O.a to O.B mil gauge was laminated to the bottom bide of the steel.
Thermal lamination was conducted at 204°C on a continuous coil steel lamination coating process.
I~fter lamination, the two-sided coated steel was cooled, wound into a roll, and later slit to 2:5 desired widths. The slit narrow web arils were later stamped into intricately shaped 25 mm diameter aerosol valve mounting cups t~VMC) using a commercial continuous 14-station multidie press. Each of the laminated structures exhibited good formability and drawability and no signs of film delarnination. The aerosol valve mounting cups were then further converted into aerosol valve assemblies by the addition of a valve, actuator and stem 30 assembly using a ~rnmercial valve assembly operation.
tfl~f~~-~~.L..1 AS's~ILS-.~
Claims (22)
1. A laminate structure comprising one or more layers of a metal and one or more layers of a hydroxy-functional polyether and, optionally, one or more layers of an organic polymer which is not a hydroxy-functional polyether, wherein said hydroxy-functional polyether layer bonds sufficiently to the metal to resist delamination from the metal layer without tearing of the hydroxy-functional polyether layer.
2. The laminate structure cf Claim 1 wherein said hydroxy-functional polyether layer exhibits a minimum of 3.5 N/cm (2.0 Ib/inch) adhesion to the metal layer.
3. The laminate structure of Claim 1 wherein said hydroxy-functional polyether layer exhibits a minimum of 5.25 N/cm (3.0 Ib/inch) adhesion to the metal layer.
4. The laminate structure of claim 7 comprising a first layer comprising a hydroxy-functional polyether, a second layer comprising metal, and a third layer comprising an organic polymer which is not a hydroxy-functional polyether, wherein the first, second and third layers are selected in any combination to form a core layer between first and second outer layers, and wherein the hydroxy-functional polyether has the structure of any of Formulas I, II, IIIa, IIIb, IVa, IVb, IVc, VIa, VIb, VIc, VII or VIII.
5. The laminate structure of claim 1 comprising a first layer comprising a hydroxy-functional polyether, a second layer comprising metal, and a third layer comprising an organic polymer which is not a hydroxy-functional polyether, wherein the first, second and third layers are selected in any combination to form a core layer between first and second outer layers, and wherein the hydroxy-functional polyether is a poly(hydroxyester ether) of Formulas VIa, VIbor VIc, or is a poly(hydroxyamino ether) of Formula VII.
6. The laminate structure of claim 1 comprising a first layer comprising a hydroxy-functional polyether, a second layer comprising metal, and a third layer comprising an organic polymer which is not a hydroxy-functional polyether, wherein the first, second and third layers are selected in any combination to form a core layer between first and second outer layers, and wherein the hydroxy-functional polyether is a poly(hydroxyamino ether) of Formula VII, and wherein said hydroxy-functional polyether layer exhibits a minimum of 3.5 N/cm (2.0 Ib/inch) adhesion to the metal layer.
7. The laminate structure of Claim 8 wherein the organic polymer which is not a hydroxy-functional polyether is polypropylene.
8. The laminate structure of Claim 1 comprising a first outer layer of a hydroxy-functional polyether, a core layer of a metal and a second outer layer of a hydroxy-functional potyether and, optionally, an adhesive layer interposed between the first outer layer and the core layer and/or between the second outer layer and the core layer.
9. The laminate structure of Claim 1 comprising a first outer layer of a hydroxy-functional polyether or a coextruded hydroxy-functional polyether/glycol-modified copolyester (PETG) film, a core layer of a metal and a second outer layer of polypropylene and, optionally, an adhesive layer interposed between the first outer layer and the core layer and/or between the second outer layer and the core layer.
10. The laminate structure of Claim 7 in the form of a three-dimensional metal structure.
11. The laminate structure of Claim 10 wherein the three-dimensional metal structure is an aerosol container, an aerosol valve mounting cup, a can bottom, a can wall, a beverage can, a food packaging can or a metal bulk packaging container.
12. The laminate structure of Claim 8 in the form of a three-dimensional metal structure.
13. The laminate structure of Claim 12 wherein the three-dimensional metal structure is an aerosol container, an aerosol valve mounting cup, a can bottom, a can wall, a beverage can, a food packaging can or a metal bulk packaging container.
14. The laminate structure of Claim 9 in the form of a three-dimensional metal structure.
15. The laminate structure of Claim 14 wherein the three-dimensional metal structure is an aerosol container, an aerosol valve mounting cup, a can bottom, a can wall, a beverage can, a food packaging can or a metal bulk packaging container.
16. The laminate structure of Claim 14 wherein the polypropylene layer is laminated to the underside of the metal and the hydroxy-functional polyether or co-extruded hydroxy-functional polyether/glycol-modified copolyester (PETG) film layer is laminated to top surface of the metal.
17. The laminate structure of Claim 7 in the form of a large metal structure.
18. The laminate structure of Claim 17 wherein the large metal structure is a refrigerator, washing machine, clothes dryer, or dishwasher.
19. The laminate structure of Claim 8 in the form of a large metal structure.
20. The laminate structure of Claim 19 wherein the large metal structure is a refrigerator, washing machine, clothes dryer, or dishwasher.
21. The laminate structure of Claim 9 in the form of a large metal structure.
22. The laminate structure of Claim 21 wherein the large metal structure is a refrigerator, washing machine, clothes dryer, or dishwasher.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US99419897A | 1997-12-19 | 1997-12-19 | |
| US08/994,198 | 1997-12-19 | ||
| PCT/US1998/022430 WO1999032281A1 (en) | 1997-12-19 | 1998-10-23 | Hydroxy-functional polyether laminates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2314243A1 true CA2314243A1 (en) | 1999-07-01 |
Family
ID=25540388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002314243A Abandoned CA2314243A1 (en) | 1997-12-19 | 1998-10-23 | Hydroxy-functional polyether laminates |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1040000A1 (en) |
| JP (1) | JP2001526130A (en) |
| KR (1) | KR20010033280A (en) |
| CN (1) | CN1282292A (en) |
| AU (1) | AU747013B2 (en) |
| BR (1) | BR9813782A (en) |
| CA (1) | CA2314243A1 (en) |
| ID (1) | ID22593A (en) |
| NZ (1) | NZ504927A (en) |
| WO (1) | WO1999032281A1 (en) |
| ZA (1) | ZA9811646B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001042008A1 (en) * | 1999-12-10 | 2001-06-14 | The Dow Chemical Company | High frequency weldable phenoxy resin films |
| ES2287046T3 (en) | 1999-12-20 | 2007-12-16 | Advanced Plastics Technologies Luxembourg S.A. | HYDROXY-FENOXIETER POLYMERS IN THE PAPER MANUFACTURE. |
| AU2002257127A1 (en) | 2001-04-04 | 2002-10-21 | Advanced Plastics Technologies, Ltd. | Process for coating paper, paperboard, and molded fiber with a water-dispersible polyester polymer |
| JP6550843B2 (en) * | 2014-03-31 | 2019-07-31 | 三菱ケミカル株式会社 | Epoxy resin, epoxy resin composition, cured product, and laminate for electric / electronic circuit |
| JP7352462B2 (en) * | 2019-01-30 | 2023-09-28 | タキロンシーアイ株式会社 | Resin film, thermoplastic carbon fiber prepreg, and manufacturing method thereof |
| GB201901503D0 (en) | 2019-02-04 | 2019-03-27 | Innospec Ltd | Chemical reactions |
| GB201901496D0 (en) | 2019-02-04 | 2019-03-27 | Innospec Ltd | Chemical reactions |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5926460A (en) * | 1982-08-06 | 1984-02-10 | 東洋製罐株式会社 | Composite material for packing vessel cover |
| EP0230099A3 (en) * | 1985-10-28 | 1988-03-16 | Mitsui Petrochemical Industries, Ltd. | Polyhydroxypolyethers, process for production thereof, and use thereof |
| KR890701661A (en) * | 1987-10-06 | 1989-12-21 | 다께바야시 쇼오고 | Polyhydroxy polyether, preparation method thereof and use thereof |
| JPH0255133A (en) * | 1988-08-19 | 1990-02-23 | Mitsui Petrochem Ind Ltd | Polyester resin laminated molded body and use thereof |
| US5164472A (en) * | 1990-01-18 | 1992-11-17 | The Dow Chemical Company | Hydroxy-functional polyethers as thermoplastic barrier resins |
-
1998
- 1998-10-23 BR BR9813782-4A patent/BR9813782A/en not_active IP Right Cessation
- 1998-10-23 JP JP2000525247A patent/JP2001526130A/en active Pending
- 1998-10-23 KR KR1020007006720A patent/KR20010033280A/en not_active Application Discontinuation
- 1998-10-23 CN CN98812429A patent/CN1282292A/en active Pending
- 1998-10-23 WO PCT/US1998/022430 patent/WO1999032281A1/en not_active Application Discontinuation
- 1998-10-23 AU AU39096/99A patent/AU747013B2/en not_active Ceased
- 1998-10-23 EP EP98967110A patent/EP1040000A1/en not_active Withdrawn
- 1998-10-23 NZ NZ504927A patent/NZ504927A/en unknown
- 1998-10-23 CA CA002314243A patent/CA2314243A1/en not_active Abandoned
- 1998-11-12 ID IDP981482A patent/ID22593A/en unknown
- 1998-12-18 ZA ZA9811646A patent/ZA9811646B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1282292A (en) | 2001-01-31 |
| NZ504927A (en) | 2001-09-28 |
| ZA9811646B (en) | 2000-06-19 |
| EP1040000A1 (en) | 2000-10-04 |
| WO1999032281A1 (en) | 1999-07-01 |
| AU3909699A (en) | 1999-07-12 |
| JP2001526130A (en) | 2001-12-18 |
| AU747013B2 (en) | 2002-05-09 |
| BR9813782A (en) | 2002-04-30 |
| KR20010033280A (en) | 2001-04-25 |
| ID22593A (en) | 1999-11-25 |
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